Kinetic studies in strongly basic glycolic solutions. Part I. The alkaline solvolysis of chloroform

Abstract

The acidity function behaviour of the alkaline solvolysis of chloroform has been investigated in the ethylene glycol (EG)–alkali-metal glycolate (MOG, M = Li, Na, and K) systems and the EG–Me₂SO–0·01M-NaOG system at 50°C. The plots of log k(k= observed rate constant) against H_ for the first three systems fall approximately on the same line, which is linear up to about 2M-NaOG with a slope of ca. 0·74, and curves down at higher concentrations. The mechanism of the reaction appears to be the same as in the aqueous and methanolic systems. The plot of log k vs. H_- for the EG–Me₂SO–001M-NaOG system is much curved but the initial slope is again ca. 0·74. The curved nature of this plot has been explained in terms of increased dispersive interaction with increase in Me₂SO content.